Demethanization of cracked gases



April '7, 1959 J. w. DAvlS N ETAL 2,880,592

DEMETHANIZATION oF CRACKED GASES Filed Nov. 10'I 1955 ATTORNEYS FEED ice

propane and higher boiling hydrocarbons contains in addi- .Y

' tion to methane large quantities of ethylene, ethane, hy-

i 2,880,592 v DEMETHANIZATION F CRACKED GASES Joseph W. Davison and Joseph R. Cobb, Ir., Bartlesville, Okla., vassgnors to Phillips Petroleum Company, a corporation of Delaware ,-'Alpplication November 10, 1955, Serial No. 546,139

6 Claims. (Cl. 62'25) This linvention relates to demethanization of a gas. In 15 one aspect it relates'toademethanization of a cracked gas containing in addition to CZ and C3 hydrocarbons con-y siderable quantities of hydrogen. In another aspect it relates to a demethanization of a gas produced by the cracking of ethane for the production of ethylene.

An object of this invention is to provide a method and apparatus for the demethanization of gases.

Another object of this invention is to provide a method and apparatus for the demethanization of cracked gases.

Still another object of our invention is to provide a method for the demethanization of a gas containing components boiling higher and at least one component 4boiling lower than methane.

Still another object of our invention is to devise a method for demethanizing a gas resulting from the cracking of ethane, propane and/ or butane, for the production of ethylene.

Still other objects and advantages of our invention will be realized upon reading the following description which, with the attached drawing, forms a part of this specitication.

The drawing is a diagrammatic representation of apparatus parts suitable for carrying out the process of our invention.

Our invention resides substantially in the combination, construction, arrangement and relative location of parts, steps and series of steps, involved in a method for demethanizing a gas comprising methane, ethylene, ethane, propylene and hydrogen, comprising chilling said gas to a temperature suciently low to condense a major portion of the C2 hydrocarbons in said gas at a superatmosphe'ric pressure, separating condensate from uncondensed gas, expanding the uncondensed gas to produce additional condensate, separating the expanded product into a gas phase rich in hydrogen and a liquid phase, combining said liquid phase with the separated condensate and fractionating the tirst mentioned condensate and liquid phase to produce an overhead product rich in methane and a kettle product rich in ethylene and ethane. y

Referring now' to the drawing, reference numerals 17',4 18 and 19 identifyUvapor-liquid separator vessels con# structed for separation of uid phases under superatmo-spheric'pressure. A feed gas, for example, produced in the cracking of ethane for the production of ethylene, after dehydration and deoiling for theremoval of propane and higher-boiling hydrocarbons, is conducted from a source, not shown, through a pipe 1 into the rst separator vessel 19. The separated vapor phase is removed through a pipe 3 and the vapor is conducted through a heat exchanger 22 operating as a cooler' from which uid passes through a pipe into the separator vessel 17. Vapor separated in this vessel is passed through a pipe 5 to `a heat exchanger 16 which serves to chill the gas from pipe 5 and chilled gas now containing some condensate is passed on through a pipe 13 into the separator vessel 18.

Such a feed stock produced in the cracking of ethane, propane and/or butane and deoiled for the removal of drogen, along with a small proportion of propylene. This gas for example at a pressure between about 700 and 900 p.s.i.a. (pounds per square inch absolute) is fed into the rst separator 19. In the example as given herein, the temperature of this feed gas after its deoilin'g anddehydration steps is about 25 F'. The cooler 22 cools this K gas to about 60 F. and Chiller 16 chills the gas from pipe 5 to about 120 F. vThe gas separated in separator 18: has a temperature of approximately 120 F. and this gas is passed through a pipe 7 to' the inlet side of a turbo:` expander 29 which operates by isentropic expansion with ,l

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the production of vuseful work. Expanded uid from th'.- turbo-expander 29 is passed lthrough a conduit 23 into al liquid gas separator 24. A

The turbo-expander 29 can able type of turbo-expander, of which the Kapitza turbine is an example of the form. The expander must be of the type capable of handling iluids containing appreciable liquid content since it is intended that an appreciable amount of liquid be condensed during the expansionstep'. Suitable forms of Kapitza turbines are disclosed in U.S. Patent 2,280,585 granted April 21, 1942. On undergoing expansion in turbine 29 with the performance of work the uid is cooled from about the aforementioned l20 F. to a temperature within the approximate range of 230 F. to -l70 F. Pressure ofthe expanded gas has been decreased from the previous high pressure to a pressure within the approximate range of 5 p.s.i.g. to 100 p.s.i.g. (pounds per square inch gauge). When the tems perature of the feed gas to the process is 25 F. and its pressure 800 p.s.i.a. the expanded uid has a tempera` ture of approximately 220 F. under 45 p.s.i.g. In sepa be any suitable and avail-,hl

The turbo-expander 29 is connected ymechanically for l driving a compressor for compressing for example ethylene of an ethylene refrigeration system 20 for the production of a refrigerant for the nal chilling step in chiller 16. This refrigeration system can be any suitable commercial refrigeration system provided it is adapted to produce adequate refrigeration. We prefer, however, to employ ethylene as the refrigerant. rlfhe cooled refrigerant from system 20 is passed through a pipe 21 to the Chiller 16 from which it returns to the compressor of the refrigeration system through a pipe 14. A

It will he obvious that all of the pipes and conduits and A' vessels in which materials in process are maintained at a subatmospheric temperature will be well insulated againstabsorption of heat from'the atmosphere.

The liquid condensates from separator tanks 19, 17 and".-

18 are removed through the respective pipes 2, 4, and 6 and are combined in pipe 30. The combined condensatesmI from separators 19, 17 and 18 are combined with the condensate from the turbo-expander separated in separator 24 and removed therefrom via a pipe 8. The total combined condensate is passed on through a pipe 10 into approximately the center vertically of a fractionator vessel 25. This fractionator vessel 2 5 is, constructed to withstand high pressures such as ordinarily utilized in bons. moved through a pipe 26 and at least a portion is condensed in condenser 27, the condensate and uncondensed materials being passed into an accumulator 31 from .the fractional distillationA of methane from C2 hydrocar- Overhead vapors from fractionator 25 are' re-' .which liquid'is passedthrough pipe 32 into `the top of the fractionator for refluxing the column. Uncondensed gas from accumulator 31 is removed as the methane product of the process through a pipe 1l for such disposalas desired. Bottomsproduct comprising ethylene,

l of ethylene, which is lost in our fractionatorv overhead methane product and208`mols in the off-gas from pipe 9. The savings accomplished by our operation over the conventional fractionation is 2,192 mols of ethylene per 24,043 mols of ethylene in the feed stock. This savings ln the material balance of The same tower pressuresv also ethane and other highjer boilinghydrocarbons such as 5 propylene, is removed/from the fractionator through a represents over 9 percent. pipe12 for such disposal as desired. Heat for reboiling the conventional fraction the fractionator employed conthe column isr provided from a heat exchanger 2d. In tains the same number of trays as the fractionator 25 emcase the operation is directed to the production or" ethylployed in our process. enethje bottoms product from pipe 12 will obviously be l0 were employed as well as the same -l20 F. overheadl fed.' into, an ethylene-ethane fractionator which is optemperature but for the conventional fractionation, there eratedin a manner to distill ethylene as an overhead was required 20,000 mols of reflux per 73,000 mols of product Vwith ethane and any other higher boiling compofeed stockin comparisonto onlyv 6,600 mols of reflux ments being separatedvas the kettle product. required to redux fractionator 25 when processing the We` iindthatordinary theturbo-expander 29 is cal5 same volume of feed stock. Dahle. Offproyidingat least most of the power for the pro- Under some conditions it is desirable to introduce the cllrctiesnuofjrejirigerationY for condensing suicient overseveral condensates and the liquid separated from the head, .j gas,in ,condenser 2,7 for` the prodnetion,` of redux expansion step separately and at diferent levels into the for the properv operation of fractionator, 25. When the, fractionator 25. In this operation liquid from. separator ethylenerefrigerationsystemHprovides this refrigeration, 20 1,9 is introduced at apoint low in the fractionator, and refrigerant fromy the system isl conducted through pipes liquids from separators 17', 13 and 24 are introduced 2 1 and 33 to the condenser 27 and the used refrigerant at successively higher points in the column. This operais transferred through pipes 34 and 14 to the inlet of 'the tion is accomplished by closing the several Valves in pipe compressor of the refrigeration system. With feed gas 30 and the valve in pipe 10, and opening the valves in to' the system at a pressure of about 800 pounds per 25 pipes 41, 42, 43 and 44. square `inch we operate fractionator at a pressure of As understood by those skilled in the art, pressure approximately 400 p.s.i.g. with a reflux temperature of regulators and pumps will need to be installed at strategic about -l20'F. and by employing these conditions, we locations to reduce pressure, and to increase pressure of areable to produce a methane product containing only uid contents of pipes and vessels when necessary. very minor amounts of higher boiling hydrocarbons. It is also noted that column 2S of our invention is As an example of the utility of our process the follownot overloaded with excessive amounts of uncondensable ing tabulation gives stream compositions of the imporhydrogen as a column would be when operating directtant intermediate and product streams ofthe process. ly on the feed stock. Temperatures and pressures are also given in the tabula- Materials of construction may be selected-fram among tion. those commercially available and adapted for use in Stream N0 (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) Mols per Day:

H2 31,661 '29s 31,362 52s aggs 372 40,464 4 30,460 1, 201 1, 201

l Redux is 6,600 mols per da Y :The ractlonator (25) is operated with a kettle temperature of 15 F. at about 400 p.s.i.g..

Stream No (15) Temp. F -60 For comparison purposes the following tabulation gives a material. balance of a fractionating column operating on` afeed stock similar to that employed in our process but without the several refrigeration and gas-liquid separation steps and also without the use of the turbo` expander, and employing only fractional distillation.

Conventional' fractionation 1 Mols Feed Overhead Kettle Product Product high pressure and low temperature applications. Corrosion resistance equipment usually is not needed since such materials as contemplated herein to be treated by our process kwill have previously been freed of corrosive components and moisture.

While certain embodiments of theinvention have been described for illustrative purposes, the invention obviously is not limited thereto.

We claim:

1. A method for demethanizing a gas comprising methane, ethylene, ethane, propylene and hydrogen comprising chilling said gas in successive chilling stages to a temperature of about -120 F. at a nal pressure of about 7 80 p.s.i.a., separating a separate liquid condensate from each of theA successive chilling steps from uncon-y densed gas, expanding said uncondensed gasto a temthe separatecondensates -at successiverlevelsin a fractional. distillation zone, the condensate'produced bythev last and lowest temperature chilling stage of said successive chilling stages being introduced into said fractional distillation zone at thi: highest level of said successive levels, introducing the condensate produced in the expanding operation into said fractionation zone at a still higher level than the highest level of said successive levels, fractionating the so-introduced condensates at a pressure of about 400 p.s.i.g. and with reux at a temperature of about -120 F. to produce an overhead product rich in methane and a kettle product rich in ethane and ethylene.

2. A method for demethanizing a gas comprising methane, ethylene, ethane, propylene and hydrogen comprising chilling said gas in successive chilling stages to a temperature suiciently low to condense a major portion of the C2 hydrocarbons in said gas at a superattnospheric pressure, separating a separate liquid condensate from each of the successive chilling steps from uncondensed gas, expanding said uncondensed g-as to produce additional condensate, separating the expanded product into a gas phase and a liquid phase, introducing the separate condensates at successive levels in a fractional distillation zone, the condensate produced by the last and lowest temperature chilling stage of said successive chilling stages being introduced into said fractional distillation zone at the highest level of said successive levels, introducing the condensate produced in the expanding operation into said fractionation zone at a still higher level than the highest level of said successive levels, fractionating the so-introduced condensates to produce an overhead product rich in methane and a kettle product rich in ethane and ethylene.

3. In the method of claim 1 operating an ethylene refrigeration system from the power obtained from the expansion step and employing the so obtained refrigeration in the iinal chilling step of the successive chilling steps.

4. In the method of claim 2 operating an ethylene refrigeration system from the power obtained from the expansion step and employing the so obtained refrigeration in the iinal chilling step of the successive chilling steps.

5. In the method of claim 1 operating an ethylene refrigeration system from the power obtained from the expansion step, condensing a portion of the overhead product rich in methane by indirect heat exchange with refrigerant ethylene, refluXing the fractionating step with the condensed methane and removing the remainder of the methane from the fractionating step as a product.

6. In the method of claim 2 operating an ethylene refrigeration system from the power obtained from the expansion step, condensing a portion of the overhead product rich in methane by indirect heat exchange with refrigerant ethylene, reuxing lthe fractionating step with the condensed methane and removing the remainder of the methane from the fractionating step as a product.

References Cited in the file of this patent UNITED STATES PATENTS 1,939,696 Hasche Dec. 19, 1933 2,134,702 Brewster Nov. l, 1938 2,224,227 Keith Dec. 10, 1940 2,265,527 Hill Dec. 9, 1941 2,265,558 Ward Dec. 9, 1941 2,274,094 Rupp Feb. 24, 1942 2,500,129 Laverty Mar. 7, 1950 2,529,312 Rupp Nov. 7, 1950 2,535,148 Martin Dec. 26, 1950 2,557,171 Bodle June 19, 1951 2,573,341 Kniel Oct. 30, 1951 2,600,494 Ferro June 17, 1952 2,619,814 Kniel Dec. 2, 1952 2,677,945 Miller May 11, 1954 2,765,635 Redcay Oct. 9, 1956 2,769,321 Stiles Nov. 6, 1956 

1. A METHOD FOR DEMETHANIZING A GAS COMPRISING METHANE, ETHYLENE, ETHANE, PROPYLENE AND HYDROGEN COMPRISING CHILLING SAID GAS IN SUCCESSIVE CHILLING STAGES TO A TEMPERATURE OF ABOUT -120* F. AT A FINAL PRESSURE OF ABOUT 870 P.S.I.A., SEPARATING A SEPARATE LIQUID CONDENSATE FROM EACH OF THE SUCCESSIVE CHILLING STEPS FROM UNCONDENSED GAS, EXPANDING SAID UNCONDENSED GAS TO A TEMPERATURE OF ABOUT -220* F. AND AT ABOUT 45 P.S.I.G. TO PRODUCE ADDITIONAL CONDENSATE, SEPARATING THE EXPANDED PRODUCT INTO A GAS PHASE AND A LIQUID PHASE, INTRODUCING THE SEPARATE CONDENSATES AT SUCCESSIVE LEVELS IN A FRACTIONAL DISTILLATION ZONE, THE CONDENSATE PRODUCED BY THE LAST AND LOWEST TEMPERATURE CHILLING STAGE OF SAID SUCCESSIVE CHILLING STAGES BEING INTRODUCED INTO SAID FRACTIONALD DISTILLATION ZONE AT THE HIGHEST LEVEL OF SAID SUCCESSIVE LEVELS, INTRODUCING THE CONDENSATE PRODUCED IN THE EXPANDING OPERATION INTO SAID FRACTIONATION ZONE AT A STILL HIGHER LEVEL THAN THE HIGHEST LEVEL OF SAID SUCCESSIVE LEVLS, FRACTIONATING THE SO-INTRODUCED CONDENSATES AT A PRESSURE OF ABOUT 400 P.S.I.G. AND WITH REFLUX AT A TEMPERATURE OF ABOUT -120* F. TO PRODUCE AN OVERHEAD PRODUCT RICH IN METHANE AND KETTLE PRODUCT RICH IN ETHANE AND THYLENE. 